水城:城市水资源的保护与利用

该文介绍了德国把城市水域重新利用开发为新的城市空间,利用滨水空间建造的高品质文化建筑,为居住之城增添许多新型城市空间的理论和实践。     

Neue Azoolefine und deren saure Spaltung zu Aryldiiminen

New Azoolefines and their Acidic cleavage to Aryldiimines 3-Amino-1-aryl-3′,3′-dimethyl-pyrazolin-4-spiro-2′-oxiran-5-ones ( 3a – c ) undergo ring opening with methoxide forming methyl 3-amino-3-arylazo-propenoates ( 5a – c ). 5a – c are cleaved under acidic conditions. The main products of the cleavage of 5c with methanolic hydrochloric acid are nitrogen, 2, 4, 6-trichloro-benzen ( 6 ), 2, 4, 6-trichloro-aniline ( 9 ) and 2, 4, 6-trichlorophenylhydrazine ( 10 ). Intermediates of the cleavage of 5 are aryldiimines trapped with benzaldehyde as the corresponding benzhydrazides ( 12a , b ).     

The Expression of Active CD11b Monocytes in Blood and Disease Progression in Amyotrophic Lateral Sclerosis

Monocytes expressing the inflammation suppressing active CD11b, a beta2 integrin, may regulate neuroinflammation and modify clinical outcomes in amyotrophic lateral sclerosis (ALS). In this single site, retrospective study, peripheral blood mononuclear cells from 38 individuals living with ALS and 20 non-neurological controls (NNC) were investigated using flow cytometry to study active CD11b integrin classical (CM), intermediate (IM) and non-classical (NCM) monocytes during ALS progression. Seventeen ALS participants were sampled at the baseline (V1) and at two additional time points (V2 and V3) for longitudinal analysis. Active CD11b+ CM frequencies increased steeply between the baseline and V3 (ANOVA repeated measurement, p < 0.001), and the V2/V1 ratio negatively correlated with the disease progression rate, similar to higher frequencies of active CD11b+ NCM at the baseline (R = −0.6567; p = 0.0031 and R = 0.3862; p = 0.0168, respectively). CD11b NCM, clinical covariates and neurofilament light-chain plasma concentration at the baseline predicted shorter survival in a multivariable and univariate analysis (CD11b NCM—HR: 1.05, CI: 1.01–1.11, p = 0.013. Log rank: above median: 43 months and below median: 21.22 months; p = 0.0022). Blood samples with the highest frequencies of active CD11b+ IM and NCM contained the lowest concentrations of soluble CD11b. Our preliminary data suggest that the levels of active CD11b+ monocytes and NCM in the blood predict different clinical outcomes in ALS.     

Ringöffnungs- und SubstitutionsReaktionen von 4,4-Dihalogen-pyrazolin-5-onen durch Nucleophile

Ring Opening and Substitution Reactions of 4,4-Dihalo-pyrazolin-5-ones with Nucleophiles 1-Aryl-4,4-dihalo-3-methyl-pyrazolin-5-ones ( 1a – c ) undergo ring opening with alkoxides and form alkyl 3-arylazo-2-halo-2-butenoats ( 2a – d ). Analogous reactions take place with ammonia and amines. 4-Nitro-phenoxide reacts with substitution of both halogens to the 4,4-bis(4-nitro-phenyl)-compound ( 5 ). Phenols are selectively orthobrominated by the title compounds 1a and b .     

An analytical solution for geotextile-wrapped soil based on insights from DEM analysis

This paper presents a novel analytical solution for geotextile-wrapped soil based on a comprehensive numerical analysis conducted using the discrete element method (DEM). By examining the soil–geotextile interface friction, principal stress distribution, and stress–strain relations of the constituent soil and geotextile in the DEM analysis, a complete picture of the mechanical characterization of geotextile-wrapped soil under uniaxial compression is first provided. With these new insights, key assumptions are verified and developed for the proposed analytical solution. In the DEM analysis, a near-failure state line that predicts stress ratios relative to the maximums at failure with respect to deviatoric strain is uniquely identified; dilation rates are found to be related to stress ratios via a single linear correlation regardless of the tensile stiffness of the geotextile. From these new findings, the assumptions on the stress-state evolution and the stress–dilatancy relation are developed accordingly, and the wrapped granular soil can therefore be modeled as a Mohr–Coulomb elastoplastic solid with evolving stress ratio and dilation rate. The development of the proposed analytical model also demonstrates an innovative approach to take advantage of multiscale insights for the analytical modeling of complex geomaterials. The analytical model is validated with the DEM simulation results of geotextile-wrapped soil under uniaxial compression, considering a wide range of geotextile tensile stiffnesses. To further examine the predictive capacity of the analytical model, the stress–strain response under triaxial compression conditions is solved analytically, taking both different confining pressures and geotextile tensile stiffnesses into account. Good agreement is obtained between the analytical and DEM solutions, which suggests that the key assumptions developed in the uniaxial compression conditions also remain valid for triaxial compression conditions.     

Investigation of ring-opening polymerization of 5-[2-{2-(2-methoxyethoxy)ethoxy}-ethoxymethyl]-5-methyl-1,3-dioxa-2-one by organometallic catalysts

To develop new polymer-based materials, the design of aliphatic carbonate has received attention and become a well-known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM-MOE3OM, were typically prepared via ring-opening polymerization (ROP) using amidine-based catalysts such as 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know-how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)-type cyclen chelating with a metal-core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM-MOE3OM upon steadily degree of polymerization.     

N-Substituted Nipecotic Acids as (S)-SNAP-5114 Analogues with Modified Lipophilic Domains

Potential mGAT4 inhibitors derived from the lead substance (S)-SNAP-5114 have been synthesized and characterized for their inhibitory potency. Variations from the parent compound included the substitution of one of its aromatic 4-methoxy and 4-methoxyphenyl groups, respectively, with a more polar moiety, including a carboxylic acid, alcohol, nitrile, carboxamide, sulfonamide, aldehyde or ketone function, or amino acid partial structures. Furthermore, it was investigated how the substitution of more than one of the aromatic 4-methoxy groups affects the potency and selectivity of the resulting compounds. Among the synthesized test substances (S)-1-{2-[(4-formylphenyl)bis(4-methoxyphenyl)-methoxy]ethyl}piperidine-3-carboxylic acid, that features a carbaldehyde function in place of one of the aromatic 4-methoxy moieties of (S)-SNAP-5114, was found to have a pIC₅₀ value of 5.89±0.07, hence constituting a slightly more potent mGAT4 inhibitor than the parent substance while showing comparable subtype selectivity.     

Ultranarrow Bandwidth Organic Photodiodes by Exchange Narrowing in Merocyanine H‐ and J‐Aggregate Excitonic Systems

Ultranarrowband organic photodiodes (OPDs) are demonstrated for thin film solid state materials composed of tightly packed dipolar merocyanine dyes. For these dyes the packing arrangement can be controlled by the bulkiness of the donor substituent, leading to either strong H‐ or strong J‐type exciton coupling in the interesting blue (H‐aggregate) and NIR (J‐aggregate) spectral ranges. Both bands are shown to arise from one single exciton band according to fluorescence measurements and are not just a mere consequence of different polymorphs within the same thin film. By fabrication of organic thin‐film transistors, these dyes are demonstrated to exhibit hole transport behavior in spin‐coated thin films. Moreover, when used as organic photodiodes in planar heterojunctions with C₆₀ fullerene, they show wavelength‐selective photocurrents in the solid state with maximum external quantum efficiencies of up to 11% and ultranarrow bandwidths down to 30 nm. Thereby, narrowing the linewidths of optoelectronic functional materials by exciton coupling provides a powerful approach to produce ultranarrowband organic photodiodes.